IR Spectros

Infrared (IR) Spectroscopy
• Infrared spectroscopy deals with the interaction of infrared radiation with matter. The IR
spectrum of a compound can provide important information about its chemical nature and
molecular structure.
• Most commonly, the spectrum is obtained by measuring the absorption of IR radiation,
although infrared emission and reflection are also used.
• Widely applied in the analysis of organic materials, also useful for polyatomic inorganic
molecules and for organometallic compounds.
Infrared region
LIMIT OF RED LIGHT: 800 nm, 0.8 µm, 12500 cm-1
NEAR INFRARED: 0.8 -2.5 µm, 12500 - 4000 cm-1
MID INFRARED: 2.5 - 50 µm, 4000 - 200 cm-1
FAR INFRARED: 50 - 1000 µm, 200 - 10 cm-1
Infrared (IR) Spectroscopy Molecular vibrations
Fundamental Vibrations
A molecule has as many degrees of freedom as the total degree of freedom of its individual
atoms. Each atom has three degrees of freedom (corresponding to the Cartesian coordinates),
thus in an N-atom molecule there will be 3N degree of freedom.
In molecules, movements of the atoms are constrained by interactions through chemical bonds.
Translation - the movement of the entire molecule while the positions of the atoms relative to
each other remain fixed: 3 degrees of translational freedom.
Rotational transitions – interatomic distances remain constant but the entire molecule rotates
with respect to three mutually perpendicular axes: 3 rotational freedom (nonlinear), 2
rotational freedom (linear).
Why not 3N-6 / 3N-5 bands in IR spectrum?

✤ The theoretical number of fundamental vibrations (absorption frequencies)
will seldom be observed
✤ Overtones (multiples of a given frequency), combination (sum of two other
vibrations) or difference (the difference of two other vibrations) tones
increase the number of bands
✤ The following effects will reduce the number of theoretical bands
✓ frequencies which fall outside the measured spectral region (400-4000 cm –1 )
✓ bands which are too weak
✓ bands are too close and coalesce
✓ occurrence of a degenerate band from several absorptions of the same frequency
✓ lack of change in molecular dipole

Vibration Types
There are two different types of vibrational modes:
Vibrations involving change in bond length- stretching vibration
Vibrations involving change in bond angle - bending vibration
Stretching
Bending
Vibrational Modes for a CH2 Group

Selection Rules
The energy associated with a quantum of light may be transferred to the
molecule if work can be performed on the molecule in the form of
displacement of charge.
Selection rule:
A molecule will absorb infrared radiation if the change in vibrational states
is associated with a change in the dipole moment (µ) of the molecule.
µ = qr
q: electrical charge, r: directed distance of that charge from some defined origin of
coordinates from the molecule.
Dipole moment is greater when electronegativity difference between the atoms in a
bond is greater.
• Vibrations which do not change the dipole moment are Infrared Inactive (eg. homonuclear
diatomics).
NB: In general, All homonuclear diatomics, like N2 and O2, cannot be detected in IR
spectroscopy.
Note that CO2 is symmetrical, and yet it creates peaks in an IR spectrum, since it has vibrational
motions (stretches and bends) that cause its dipole moment to shift.
Infrared Spectrum of Carbon Dioxide
Note:
1. No. of fundamental vibration
= vibrational degrees of freedom
=9-5=4
2. Both the bending modes have

same frequency
symmetric stretching (IR inactive) asymmetric stretching (2350 cm-1)
in-plane bending (666 cm-1)
out-of-plane bending (666 cm-1)

Infrared Spectrum of Water

Vibrational spectra (I): Harmonic oscillator model
Hooke’s Law
Vibrational spectra (II): Anharmonic oscillator model
The actual potential energy

of vibrations fits the
parabolic function fairly well
only near the equilibrium
internuclear distance. The
Morse potential function
more closely resembles the
potential energy of vibrations
Fig. 12-1 in a molecule for all
internuclear distances-
anharmonic oscillator model.
Vibrational spectra (III): Rotation-vibration transitions

The vibrational spectra appear as bands rather than lines. When vibrational
spectra of gaseous diatomic molecules are observed under high-resolution
conditions, each band can be found to contain a large number of closely
spaced components— band spectra. The structure observed is due to that a
single vibrational energy change is accompanied by a number of rotational
energy changes. The form of such a vibration-rotation spectrum can be
predicted from the energy levels of a vibrating-rotating molecule.
–> “vibrational-rotational bands”
A vibrational absorption transition from υ to υ+1 gives rise to three sets

of lines called branches:
Lower-frequency P branch: Δυ=1, ΔJ=-1;
Higher-frequency R branch: Δυ=1, ΔJ=+1;
Rotation-vibration transitions
P R
• The selection rules allow only transitions with Δν = +1 and ΔJ = ±1 (the

transition with ΔJ = 0 is normally not allowed except those with an odd number
of electrons (e.g. NO)).
Region of Functional Group Vibrations vs Fingerprint Region
✤ An infrared spectrum of an organic compound comprises many bands and assigning each
band to a particular mode of vibration is practically impossible but two non-identical
molecules generally have different IR spectra.
✤ An IR spectrum, therefore, is a fingerprint of the molecule. The region most useful for the
purpose of “fingerprinting” of the compound is 650-1350 cm-1. This region comprises a
large number of bands due to skeletal vibrations and when the spectrum we are studying
coincides exactly with the spectrum of a known compound, it can be safely assumed that the
two compounds are identical.
✤ The region above 1350 cm-1 often provides easily recognizable bands of various functional
groups and thus much valuable structural evidence from relatively few of theses bands is
obtained and total interpretation of the complete spectrum is seldom required. In the
following sections, the basic information about the vibrational modes in basic functional
groups has been discussed.
Fingerprint Region
✓ In the region from ≈ 1300 to 400 cm-1, vibrational frequencies are affected by the entire molecule, as the broader ranges
for group absorptions in the figure below – fingerprint region.
✓ Absorption in this fingerprint region is characteristic of the molecule as a whole. This region finds widespread use for
identification purpose by comparison with library spectra.
Group frequencies
With certain functional or structural groups, it has been found that
their vibrational frequencies are nearly independent of the rest of the
molecule – group frequencies.
Carbonyl group 1650 to 1740 cm-1 various aldehydes and ketones
Calculations show that for most groups of interest, characteristic

frequencies of stretching vibrations should lie in the region 4000 to 1000
cm-1.
In practical, the region from 4000 to 1300 cm-1 is often called the group
frequency region.
✤ The presence of various group vibrations in the IR spectrum is of great

assistance in identifying the absorbing molecule.
Absorption Regions
Factors Influencing Vibrational Frequencies

1. Higher the force constant, larger the vibrational frequency
2. Lighter the atoms connected, higher the frequency
3. The vibrational frequency of a bond, being part of a molecule, is significantly affected by the
electronic and steric factors of the surroundings, in addition to the bond strength and atomic
masses discussed above.
When two bond oscillators share a common atom, they seldom behave as individual oscillators
where the individual oscillation frequencies are widely different. The mechanical coupling
interactions between two oscillators are responsible for these changes.
For example, the carbon dioxide molecule, which consists of two C=O bonds with a common
carbon atom, has two fundamental stretching vibrations – an asymmetrical and a symmetrical
stretching mode. The symmetrical stretching mode produces no change in dipole moment and is
IR inactive. Asymmetric stretching mode is IR active and appears at a higher frequency (2350
cm-1) than observed for a carbonyl group in aliphatic ketones (1715 cm-1).

Higher the force constant, larger
the vibrational frequency
Stretching vs bending vibrational frequency

Alkanes: C-H and C-C Vibrations

✴ In simple hydrocarbons, only two types of atoms – C and H and only two types of bonds – C-C and C-H
are present.
✴ C-H Stretching:
✴ C-H Bending: The C-H bending vibrations of the methyl groups in the hydrocarbons normally occur at
1450 (scissoring) and 1375 (rocking) cm-1
✴ In case of methylene group, C-H bending vibrations normally appear at fairly different frequencies. If
two or more CH2 groups are present, the usually strong scissoring and rocking absorption bands appear
at 1465 and 720 cm-1, respectively. Whereas weak bands due to twisting and wagging vibrations appear
at 1250 + 100 cm-1. So, the scissoring absorption band of methylene around 1465 cm-1 often overlaps
with asymmetric bending vibration of methyl at 1450 cm-1.
✴ The C-C bond vibrations appear as weak bands in 1200-800 cm-1 region and are seldom used for structural
study. Whereas the C-C bending absorptions occur at < 500 cm-1 and are usually below the range of IR –
instrument.
Alkanes
C-H str.
Cyclo Alkanes
Alkenes: C-H and C=C Vibrations

Acyclic Alkenes: C=C stretching of conjugated double bond

Cyclic Alkenes: C=C Stretching vibration in endocyclic systems

✴ The absorption frequency of a double bond in a cyclic ring is very sensitive to ring size.
✴ The absorption frequency decreases as the internal angle decreases and is lowest in cyclobutene
(90o angle). The frequency increases again for cyclopropane.
Exception
Cyclic Alkenes: C=C Stretching vibration in endocyclic systems

1.
Effects of Alkyl Substitutions

Cyclic Alkenes: C=C Stretching vibration in exocyclic systems

✴ The exocyclic double bonds exhibit an increase in frequency with decrease in ring size.
✴ The exocyclic double bond on six-membered ring absorbs at 1651 cm-1 and it is shifted to 1780 cm-1 in
case of exocyclic double bond on cyclopropane. The allenes show the highest double bond absorptions at
1940 cm-1
Alkynes: C-H and C C Vibrations

Aromatic Rings: C-H and C=C Vibrations

Infrared (IR) Spectroscopy Aromatic Rings
Alcohols and Phenols: O-H and C-O Vibrations

Alcohols and Phenols: O-H and C-O Vibrations

Ethers: C-O Vibrations

Carbonyls: C=O Vibrations C O
Factors that influence carbonyl stretching frequency

(i) Electronic effects of neighbouring substituents
(ii) Resonance effects ( both C=C and heteroatom lone pair)
(iii) Hydrogen bonding (inter and intramolecular)
(iv) Ring strain etc.
It is customary to refer to the absorption frequency of a saturated aliphatic ketone at 1715 cm-1
as normal value and changes in the environment of the carbonyl group can either lower or raise
the absorption frequency from the “normal” value.
Carbonyls: C=O Vibrations
✤ The replacement of an alkyl group of the saturated aliphatic ketone by a ‘H’ -

shifts the C=O stretching frequencies to a higher value due to reduction of +I
effect by alkyl group.
Aldehydes and ketones
✤ In esters, the oxygen due to inductive effect withdraws the electrons from carbonyl
group and increases the C=O bond strength and thus the frequency of absorption.
Esters
✤ The acid anhydrides give two bands in C=O stretching frequency region
due to symmetric (~ 1760 cm-1) and asymmetric (~1820 cm-1) stretching
vibrations.
Anhydrides
✤ In acid chlorides, the halogen atom strengthens the C=O bond through inductive effect and
shifts the C=O stretching frequencies even higher than are found in esters.
Acid chlorides
Carboxylic acid
✤ Dimerisation weakens the C=O bond strength thus reduces the C=O absorption frequency. Therefore, C=O
absorption frequencies in carboxylic acid is comparable with ketones.
Amides
✤ In amides, due to the conjugation of lone pair of electrons on nitrogen atom, the resonance effect increases
the C=O bond length and reduces the C=O absorption frequency. Therefore, C=O absorption frequencies
due to resonance effects in amides are lowered but due to inductive effect in esters are increased than those
observed in ketones.
Ketones: C=O Vibrations

Aldehydes: C=O Vibrations

Esters: C=O Vibrations

Anhydride: C=O Vibrations

Acid Chloride: C=O Vibrations

Carboxylic Acid: C=O Vibrations

1710 cm-1
Amides: C=O Vibrations


Other Factors that influence Carbonyl Stretching Frequency





Effect of Hydrogen Bonding

Correlation Chart

IR Spectros

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IR Spectros

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Infrared (IR) Spectroscopy

Why not 3N-6 / 3N-5 bands in IR spectrum?

✓ bands which are too weak

✓ bands are too close and coalesce

✓ occurrence of a degenerate band from several absorptions of the same frequency

✓ lack of change in molecular dipole

Vibrational Modes for a CH2 Group

Infrared Spectrum of Carbon Dioxide

2. Both the bending modes have

symmetric stretching (IR inactive) asymmetric stretching (2350 cm-1)

in-plane bending (666 cm-1)

out-of-plane bending (666 cm-1)

Infrared Spectrum of Water

Vibrational spectra (I): Harmonic oscillator model

The actual potential energy

Vibrational spectra (III): Rotation-vibration transitions

A vibrational absorption transition from υ to υ+1 gives rise to three sets

• The selection rules allow only transitions with Δν = +1 and ΔJ = ±1 (the

Region of Functional Group Vibrations vs Fingerprint Region

Calculations show that for most groups of interest, characteristic

✤ The presence of various group vibrations in the IR spectrum is of great

Factors Influencing Vibrational Frequencies

2. Lighter the atoms connected, higher the frequency

Factors Influencing Vibrational Frequencies

Factors Influencing Vibrational Frequencies

Stretching vs bending vibrational frequency

Alkanes: C-H and C-C Vibrations

Alkenes: C-H and C=C Vibrations

Acyclic Alkenes: C=C stretching of conjugated double bond

Cyclic Alkenes: C=C Stretching vibration in endocyclic systems

Cyclic Alkenes: C=C Stretching vibration in endocyclic systems

Effects of Alkyl Substitutions

Cyclic Alkenes: C=C Stretching vibration in exocyclic systems

Alkynes: C-H and C C Vibrations

Aromatic Rings: C-H and C=C Vibrations

Alcohols and Phenols: O-H and C-O Vibrations

Alcohols and Phenols: O-H and C-O Vibrations

Ethers: C-O Vibrations

Carbonyls: C=O Vibrations C O

Factors that influence carbonyl stretching frequency

Carbonyls: C=O Vibrations

✤ The replacement of an alkyl group of the saturated aliphatic ketone by a ‘H’ -

Carbonyls: C=O Vibrations

Ketones: C=O Vibrations

Aldehydes: C=O Vibrations

Esters: C=O Vibrations

Anhydride: C=O Vibrations

Acid Chloride: C=O Vibrations

Carboxylic Acid: C=O Vibrations

Amides: C=O Vibrations

Carbonyls: C=O Vibrations

Carbonyls: C=O Vibrations

Other Factors that influence Carbonyl Stretching Frequency

Carbonyls: C=O Vibrations

Carbonyls: C=O Vibrations

Carbonyls: C=O Vibrations

Effect of Hydrogen Bonding

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